Novel compounds with detergency and fabric-softening ability and method of making the same

ABSTRACT

gas phase, at elevated temperature and in contact with a carrier catalyst, the reaction being carried out in contact with a carrier catalyst containing palladium acetate, alkali metal acetate and one or more uranium compounds as its active constituents.

United States Patent 72] Inventor Bjorn Sundby Highland Park, NJ.

[21] Appl. No. 780,276

122] Filed Nov. 29, 1968 [45] Patented Dec. 14, 1971 [73] AssigneeColgate-Palmolive Company New York, N.Y.

[54] NOVEL COMPOUNDS WITH DETERGENCY AND FABRIC-SOFIENING ABILITY ANDMETHOD OF MAKING THE SAME 15 Claims, No Drawings 260/501.12, 260/609 F,260/615 R, 424/70, 424/56, 424/303, 252/161, 117/139.5 CO [51] Int. Cl..C07c143/l0 [50] Field of Search 260/513 B, 513,615,607 A,513 R [56]References Cited UNITED STATES PATENTS 2,913,324 11/1959 Kosmin 260/5133,086,043 4/1963 Gaertner 260/513 2,427,577 9/1947 Smith 260/5133,082,249 3/1963 Gaertner 260/513 8 Swern et al., J. Am. Chem. Soc. 71,1 1 52 1949).

Primary Examiner- Daniel D. Horwitz Attorneys-Herbert S. Sylvester,Murray M. Grill, Norman Blumenkopf, Ronald S. Cornell, Thomas J. Corum,Richard N. Miller and Robert L. Stone ABS BAQBMYQE WPQHQQ M; fo mu[Rs-Il OH RQJX wherein (1) R is a straight or branched higher alkylgroup of C to Q and preferably C to C NOVEL COMPOUNDS WITH DETERGENCYAND FABRIC-SOFTENING ABILITY AND METHOD OF MAKING THE SAME The presentinvention relates to novel compounds uniquely containing foaming anddetergency properties in addition to fabric-softening ability, methodsof preparing the same, and novel intermediate compounds useful in theirpreparation. More particularly, the present invention relates to suchnovel compounds of the hydroxy ether (including thioether) sulfonatetype.

While in recent years various outstanding detergent materials andvarious outstanding softening agents have been developed, it has stillbeen necessary to provide separate materials for performing these twofunctions. Thus, until the present invention no successful detergentmaterial possessing softening ability has been discovered.

The most successful detergents developed in recent years are the linearalkyl benzene sulfonates. While such materials possess excellent foamingand detergency characteristics such materials possess little or nosoftening ability.

The most efi'ective softeners that have been developed in recent yearsare the quaternary ammonium fabric-softening agents. While thesecationic agents are extremely effective in the softening of textilefabrics, it is noted that, because of their cationic nature, suchfabric-softening additives cannot be employed in conjunction withconventional anionic detergents, e.g. sulfonates, and therefore, must beadded to the wash water during the rinse cycle operation. This is due tothe fact that the cationic quaternary ammonium fabric softeners andanionic detergents complex and precipitate thus adversely effecting theoperability of each of the materials.

Accordingly, in accordance with previous materials and methods, the useof separate detergents and fabric softeners has been even morecomplicated by the incompatability of the best detergents and fabricsofteners previously available.

Therefore, it has been the long desire of the detergent in- 'dustry toprovide a single compound possessing the foaming detergencycharacteristics of conventional detergents, yet uniquely possessingfabric-softening ability. Such a single compound uniquely possessingboth detergency and fabricsoftening ability would of course eliminatethe disadvantages of employing two separate materials, and, in addition,would completely eliminate the disadvantages associated with theincompatability of conventional anionic detergents and cationic fabricsofteners.

In accordance with the present invention, it has now been discoveredthat certain hydroxy ether sulfonates possess detergency characteristicssubstantially equivalent to or better than that of conventional anionicdetergents now employed in detergent compositions and, in addition,possess fabric-softening ability substantially equivalent to quaternaryammonium cationic fabric softeners now conventionally employed in therinse cycle of a washing operation.

It is therefore a principle object of the present invention to provide adetergent compound possessing fabric-softening ability.

It is a further object of the present invention to provide such a noveldetergent compound possessing fabric-softening ability which novelcompound eliminates the previous deficiencies associated with theemployment of separate incompatible detergents and fabric softeners.

A yet further object of the present invention is to provide certainnovel hydroxy ether sulfonates which possess detergent and foamingcharacteristics substantially equivalent to or superior to conventionalanionic detergents and fabric-softening ability substantially equivalentto conventional cationic quaternary ammonium softeners.

Still a further object of the present invention is to provide novelmethods of producing certain hydroxy ether sulfonates possessing bothdetergency and fabric-softening ability, such processes including thereaction of an unsaturated alcohol with a long-chain epoxide withsubsequent sulfonation of the reaction product.

Yet a further object of the present invention is to provide novelunsaturated hydroxy ethers useful as intermediates in the production ofthe hydroxy ether sulfonates of the present invention.

Still another further object of the present invention is the provisionof novel hydroxy ether sulfonates which are compatible with buildersalts and particularly tetrapotassium pyrophosphate in aqueous systemsobviating the need for hydrotropic agents.

Still further objects and advantages of the novel compounds and processof the present invention will become more apparent from the followingmore detailed description thereof.

The novel compounds of the present invention which uniquely possessoutstanding foaming and detergency characteristics in addition tofabric-softening ability correspond to the general formula:

wherein:

l. R, is a straight or branched higher alkyl group of C to C andpreferably C to C 2. R, is a straight or branched alkylene of C to C andpreferably C to C 3 R to R are, independently, hydrogen or straight orbranched alkyl of C to C and preferably hydrogen or lower alkyl of C toC 4. Z is oxygen (-0-) or sulfur (S);

5. x and y have the values 0 or 1 and x-i-y=l and 6. M is a cation suchas hydrogen, alkali metal, ammonium, substituted ammonium or amine andpreferably a water-solubilizing, salt-forming group.

While the sodium salts of the hydroxy ether sulfonates of the presentinvention are preferred, it is of course possible to advantageouslyemploy other alkali metals such as potassium or lithium. Additionally,ammonium and amine salts, e.g., trialkanolamine salts such astriethanolamine can be advantageously employed with exceptional results.

The novel hydroxy ether sulfonates of the present invention may beprepared by reacting an epoxy alkane with an unsaturated aliphaticalcohol with subsequent sulfonation of the reaction product. The epoxyalkane reactants that are useful in the preparation of the hydroxy ethersulfonates of the present invention can be any epoxy alkane having aterminal group i.e., an epoxy alkane having the structure:

wherein R, is as defined above. As noted above, R comprises a straightor branchedchain alkyl. radical of from about six to about 30 carbonatoms. Illustrative examples of some suitable alkyl radicals include:

n-hexyl iso-hexyl iso-heptyl n-octyl iso-octyl n-nonyl iso-nonyl n-decyln-dodecyl tertedodecyl 2-propylheptyl S-ethylnonyl 2-butyloctyln-undecyl n-tridecyl n-tetradecyl n-pentadecyl tert-octadecyl2,6,8-trimethylnonyl v 7-ethyl-2-methy1-4-undecyl n-hexadecyln-octadecyl eicosyl docosyl tricosyl pentacosyl triacontyl etc.

The alkyl radicals may also include unsaturated alkyl radicals such ashexenyl, oleyl, dodecenyl, hexadecenyl, and the like.

Illustrative examples of some epoxy alkanes which can be employed asreactants in the process of the present invention to produce the novelhydroxy ether sulfonates of the present invention include:

1,2 epoxyhexane 1,2 epoxyoctane 1,2 epoxydecane 1,2 epoxyundecane 1.2epoxydodecane 1,2 epoxytridecane 1,2 epoxytetradecane 1,2epoxypentadecane 1,2 epoxyhexadecane 1,2 epoxyoxtadecane7-ethyl-2-methy1- 1 ,2-epoxyundecane 2,6,8-trimethy1-1,2-epoxynonanel,1,2-trimethyl-1.2-epoxy decane 1,1-dimethyl-2-ethy1--epoxy decane-epoxy decane l-methy1-1,2-diethyl-l ,2-epoxy tetradecane 1 l -dimethy1epoxy undecane 1, l -diethyl epoxy decane 1,1diisopropy1 epoxy octaneetc.

Exemplary hydroxy ether sulfonates in accordance with the presentinvention include:

A. Oxa derivatives 1. wherein v==l and x= 6-hydroxy-4-oxahexadecylsodium sulfonate 6-hydroxy-4oxaheptadecyl sodium sulfonate6-hydroxy-4-oxaoctadecyl sodium sulfonate 6-hydroxy-4-oxanonadecylsodium sulfonate 6-hydroxy-4-oxaeicosyl sodium sulfonate6-hydroxy-4-oxauncosyl sodium sulfonate 6-hydroxy-4-oxadocosyl sodiumsulfonate 6-hydroxy-8-methyl-12-ethyl-4-oxapentadecyl sodium sulfonate6-hydroxy-7,7-dimethyl-4-oxahexadecyl sodium sulfate6-hydroxy-4-oxatetracosyl sodium sulfonate 6-hydroxy-4-oxahexadecylpotassium sulfonate 6-hydroxy-4-oxaheptadecyl potassium sulfonate6-hydroxy-4-oxaoctadecyl potassium sulfonate 6-hydroxy-4-oxanonadecylpotassium sulfonate 6-hydroxy-4-oxaeicosyl potassium sulfonate6-hydroxy-4-oxauncosyl potassium sulfonate 6-hydroxy-4-oxadocosylpotassium sulfonate 6-hydroxy-8 methyll2-ethyl-4-oxapentadecyl potassiumsulfonate 6-hydroxy-7,7-dimethyl-4-oxahexadecyl potassium sulfonate6-hydroxy-4-oxatetracosyl potassium sulfonate 6-hydroxy-4-oxahexadecyllithium sulfonate 6-hydroxy-4-oxaoctadecyl lithium sulfonate6-hydroxy-4-oxanonadecyl lithium sulfonate 6-hydroxy-4-oxadocosyllithium sulfonate 6-hydroxy-4-oxahexadecyl ammonium sulfonate6-hydroxy-4-oxaheptadecyl ammonium sulfonate 6-hydroxy-4-oxaeicosy1ammonium sulfonate 6-hydroxy-4-oxadocosyl ammonium sulfonate 6-hydroxy-8methyl-l2-ethyl-4-oxapentadecyl ammonium sulfonate triethanol amine saltof 6-hydroxy-4-oxahexadecyl sulfonic acid triethanol amine salt of6-hydroxy-4-oxaheptadecyl sulfonic acid triethanol amine salt of6-hydroxy-4-oxaeicosyl sulfonic acid triethanol amine salt of6-hydroxy-7,7-dimethyl-4-oxahexadecyl sulfonic acid.

8-hydroxy-6-oxahexadecyl sodium sulfonate 8-hydroxy-6-oxaheptadecylsodium sulfonate 8-hydroxy-6-oxaoctadecyl sodium sulfonate8-hydroxy-6-oxanonadecyl sodium sulfonate 8-hydroxy-6-oxaeicosyl sodiumsulfonate 8-hydroxy-6-oxauncosyl sodium sulfonate 8-hydroxy-6-oxadocosylsodium sulfonate 8-hydroxy-8 methyl-12-ethyl-6-oxapentadecyl sodiumsulfonate 8-hydroxy-1 1,1 1, dimethyl-6-oxahexadecyl sodium sulfonate8-hydroxy-6-oxatetracosy1 sodium sulfonate 8-hydroxy-6-oxahexadecy1potassium sulfonate 8-hydroxy-6-oxaheptadecyl potassium sulfonate8-hydroxy-6-oxaoctadecyl potassium sulfonate 8-hydroxy-6-oxanonadecylpotassium sulfonate 8-hydroxy-6-oxaeicosyl potassium sulfonate8-hydroxy-6-oxauncosyl potassium sulfonate 8-hydroxy-6-oxadocosylpotassium sulfonate 8-hydroxy-8 methyl-l2-ethyl-6-oxapentadecylpotassium sulfonate 8-hydroxy-1 1,1 l-dimethyl-6-oxahexadecyl potassiumsulfonate 8-hydroxy--oxatetracosyl potassium sulfonate8-hydroxy6-oxahexadecyl lithium sulfonate 8-hydroxy-6-oxaoctadecyllithium. sulfonate 8-hydroxy-6-oxanonadecyl lithium sulfonateS-hydroxy-fi-oxadocosyl lithium sulfonate 8-hydroxy-6-oxahexadecylammonium sulfonate 8-hydroxy-6-oxaheptadecyl ammonium sulfonate8-hydroxy-6-oxaeicosy1 ammonium sulfonate 8-hydroxy-6-oxadocosylammonium sulfonate 8-hydroxy-8 methyl-12-ethy1-6-oxapentadecyl ammoniumsulfonate triethanol amine salt of 8-hydroxy-6-oxahexadecy1 sulfonicacid triethanol amine salt of 8-hydroxy 6-oxaheptadecyl sulfonic acidtriethanol amine salt of 8-hydroxy-6-oxaeicosyl sulfonic acid triethanolamine salt of 8-hydroxy-9,9-dimethyl-6-oxahexadecyl sulfonic acid7-hydroxy-5-oxahexadecyl sodium sulfonate 7-hydroxy-5-oxaoctadccylsodium sulfonate 7-hydroxy-5-oxaeicosyl sodium sulfonate7-hydroxy-5-oxadocosyl sodium sulfonate7-hydroxy-9,9-dimethyl-5-oxahexadecyl sodium sulfonate7-hydroxy-5-oxahexadecyl potassium sulfonate 7-hydroxy-5-oxaoctadecylpotassium sulfonate 7-hydroxy-5-oxaeicosyl potassium sulfonate7-hydroxy-5-oxadocosyl potassium sulfonate7-hydroxy-9,Q-dimethyl-5-oxahexadecyl potassium fonate7-hydroxy-5-oxahexadecyl lithium sulfonate 7-hydroxy-5-oxanondecyllithium sulfonate 7-hydroxy-5-oxahexadecyl ammonium sulfonate7-hydroxy-5-oxaeicosyl ammonium sulfonate 7-hydroxy-8methyl-12-ethy1-5-oxapentadecy1 ammonium sulfonate triethanol amine saltof 7-hydroxy-5-oxaheptadecyl sulfonic acid triethanol amine salt of7-hydroxy-7,7-dimethyl-5oxahexadecyl sulfonic acid10-hydroxy-8-oxahexadecyl sodium sulfonate sul-3,5-dimethyl--hexene-3-thiol 2,3-diemthyl-4-pentene-2-thiol3-ethyl-5-hexene-3-thiol l-heptene-3-thiol 2-heptene-4-thiol 3-heptenel-thiol 4-hexene-3-thiol 5-hexene-3-thiol 3-methyl-3-butene-2-thiolZ-methyll -heptene-3-thiol 3-methyl-5-hexene-3-thiol 2-methyll-pentene-3-thiol 2-methyl-4-pentene-3-thiol 4-methyll -pentene-3-thiol4-methyl-3-pentene-2-thiol lO-undecenel -thiol The hydroxy ether orthioether sulfonates of the present invention are prepared, using onetechnique, by the reaction of long-chain epoxide with an unsaturatedalcohol or thioalcohol (Le. mercaptan) with subsequent sulfonation ofthe intermediate product in accordance with the following equations.illustrating the use of an alcohol:

wherein R is as defined above; and R is C to C which together with CH-CHforms an unsaturated group within the scope of R,,.

Reaction 1 above is preferably catalyzed by the employment of sodium,preferably dissolved in the alcohol reactant. Thus, while it has beenestablished that almost quantitative yields of the unsaturatedintermediate product can be produced by the use of sodium as thecatalyst in the process of the present invention, it is, of course,obvious that any catalyst material capable of effecting the condensationof the alcohol and longchain epoxide with the opening of the epoxy ringcan be successfully employed in the process of the present invention.Such exemplary catalysts include for example BF BF -dialkyl etherate,etc.

The reaction of the long-chain epoxide and alcohol is not criticallydependent upon the choice of temperature, pressure or amount ofreactants, Thus, while the epoxide and alcohol react in substantiallystoichiometric proportions, it is possible to employ a relatively largeexcess of either the long-chain epoxide or the alcohol reactant withoutadversely effecting the reaction system. in this respect, it has beenshown that the employment of such a relatively large excess of eitherreactant merely necessitates removal of the excess reactant from thereaction system and does not adversely efiect the product or yieldthereof.

Similarly, it has been found that the reaction of the present inventioncan be suitably run at ambient pressure or under increased pressureconditioi'is, the pressure of the system having relatively little effectupon the yield and purity of the intermediate product and final productproduced. For economic purposes however, it has been found most suitableto run the reaction under atmospheric pressure conditions.

Similarly, it has been determined that the temperature at which thereaction is run is not critical with respect to the purity and yield ofboth the intermediate product and the final product in accordance withthe process of the present invention. Thus. temperatures ranging fromambient temperatures up through approximately 150 C. have been foundsuitable in accordance with the process of the present invention,although any temperature may be used provided the reactants are stablethereat. The selection of any particular temperature will be dependent,inter alia, upon the specific reactants and the selection of catalyst,if any, employed. Suitable catalysts include any basic or acidicmaterial. Illustrative catalysts are alkali metals, alkalihydroxides,Lewis acids such as boron trifluoride, aluminum chloride, etc. Thecatalyst concentration is not critical, and as little as 0.001 percentmay be used; the upper limit may be 10 percent.

It is pointed out that while the above description has been directedprimarily to the employment of a single long-chain epoxide in thereaction with alcohol to produce a single unsaturated hydroxy etherintermediate product, it is of course obvious that mixtures of suchlong-chain epoxides can be suitably employed to produce a mixture ofsuch unsaturated hydroxy ethers. The sulfonation of such mixture ofproducts will produce a mixture of hydroxy ether sulfonates whichmixture is exceptionally useful because of its detergency andfabric-softening ability. Accordingly, a suitable reaction mixture oflong-chain epoxides has been found to be a mixture of C, C,,, l ,2-epoxyalkanes.

it is within the contemplation of the present invention to carry out theprocesses for producing the compounds of this invention, including thel2-epoxyalkane-alcohol condensation reaction in the presence of inertdiluent or mutual nonreactive solvents such as xylene, toluene, etc.,and in the sulfonation phase of the process there may also be usedaqueous alcohols e.g., aqueous methanol, ethanol, n-propanol,isopropanol, butanol, pyridine, etc.

The novel unsaturated hydroxy ether intermediate prepared by thereaction of the long-chain epoxide and unsaturated alcohol can besulfonated to produce the novel detergent and 0 fabric-softeningcompounds of the present invention in any suitable conventional manner.Thus, it has been found convenient to sulfonate the double bond of thenovel intermediate compound with a bisulfite e.g., sodium bisulfite inthe presence of an initiator. Suitable initiators include peroxideinitiators include for example tertiary butyl perbenzoates, di-tbutylperoxide, dibenzoyl peroxide, dilauryl peroxide, etc.'(' Anotherinitiator system is the nitrate/oxygen system eg potassium nitrate,lithium nitrate ammonium nitrate, alkaline earth nitrates and others,whichdo not accelerate bisulfite oxidation to sulfate in the presence ofoxygen, preferably at a partial pressure of from I to 1.5 psi) Such aprocess which is conveniently employed in the sulfonation of doublebonds is set forth in U.S. Pat. No. 2,504,4l l, the subject matter ofwhich is incorporated herein by reference. While the temperature of thesulfonation reaction is not critical, generally slightly elevatedtemperatures are employed. Thus, for example, a temperature of fromabout 40 to C. can be conveniently employed in the sulfonation of thenovel unsaturated hydroxy ether compounds of the present invention.

Other synthetic routes may be used. For example, in place of theunsaturated alcohol, one may condense the epoxy alkane with an a,w-halohydroxy compound, dehydrohalogenate and then sulfonate withbisulfite, or alternatively employ sodium sulfite (in lieu ofdehydrohalogenation and bisulfite), i.e., Strecker reaction. Furthervicinal glycols reacted with sultones yield the instant compounds.

The novel hydroxy ether sulfonates of the present invention, in additionto possessing excellent detergency and fabric-softening properties, havebeen found to be compatible with the various detergent builders andother additives conventionally employed in detergent compositions.Accordingly, it is possible to formulate a detergent composition basedupon the hydroxy ether sulfonate as the detergent and fabric softener.Because of the unusual compatibility of the hydroxy ether sulfonates ofthe present invention with the various detergent builders, it ispossible to prepare both solid-phase detergent compositions andsingle-phase liquid detergent compositions which could not be suitablyprepared with the employment of conventional linear alkyl benzenesulfonates.

The new compounds of this invention and the new mixtures containing suchcompounds may be employed in a wide variety of detergent compositions,including light-duty liquid detergent formulations and granularcompositions such as spray-dried built detergent powders. They may beused in toilet bars for washing the hands, face and body (here, as inother formulations, their unexpected germicidal properties are highlyadvantageous) or in laundry detergent bars, containing appreciableamounts of builder salts, for washing clothes. They may also be used inhair-shampooing, hair-dyeing or other hair-treating or hair-conditioningcompositions. They may also be used in dental creams or otherdentifrices and in skin care preparations such as creams and lotions.

The novel detergent compounds of this invention may be used as such oras mixtures with other surface-active detergents. The addedsurfaceactive detergents may be of the anionic, nonionic, cationic oramphoteric types, or mixtures thereof.

The anionic surface active agents include those surface active ordetergent compounds which contain an organic hydrophobic group and ananionic solubilizing group. Typical examples of anionic solubilizinggroups are sulfonate, sulfate, carboxylate, phosphonate and phosphate.Examples of suitable anionic detergents which fall within the scope ofthe invention include the soaps, such as the water-soluble salts ofhigher fatty acids or rosin acids, such as may be derived from fats,oils and waxes of animal, vegetable or marine origin, eg the sodiumsoaps of tallow, grease, coconut oil, tall oil and mixtures thereof; andthe sulfated and sulfonated synthetic detergents, particularly thosehaving about eight to 26, and preferably about 12 to 22, carbon atoms tothe molecule.

As examples of suitable synthetic anionic detergents there may be citedthe higher alkyl mononuclear aromatic sulfonates such as the higheralkyl benzene sulfonates containing from to 16 carbon atoms in the alkylgroup in a straight or branched chain, e.g., the sodium salts of higheralkyl benzene sulfonates or of the higher alkyl toluene, xylene andphenol sulfonates; alkyl napthalene sulfonate, ammonium diamylnapthalene sulfonate, and sodium dinonyl napthalene sulfonate. In onepreferred type of composition there is used a linear alkyl 1 sulfonatehaving a high content of 3-(or higher) phenyl isomers and acorrespondingly low content (well below 50 percent of 2-( or lower)phenyl isomers; in other terminology, the benzene ring is preferablyattached in large part at the 3 or higher (e.g. 4, 5, 6 or 7) positionof the alkyl group and the content of isomers in which the benzene ringis attached at the the 2 or 1 position is correspondingly low.Particularly preferred materials are set forth in US. Pat. No.3,320,174, May 16, 1967, OH. Rubinfeld.

The mixtures containing linear alkylbenzene sulfonates and the detergentcompounds of this invention have unexpectedly good properties,particularly with respect to softening power. These mixtures are theinvention of Harold Wixon.

Other anionic detergents are the olefin sulfonates, including long-chainalkene sulfonates, long-chain hydroxyalkane sulfonates or mixtures ofalkenesulfonates and hydroxyalkanesulfonates These olefin sulfonatedetergents may be prepared, in known manner, by the reaction of 80;,with long chain olefins (of 8 to 25, preferably 12-21 carbon atoms) ofthe formula R'CH-CHR", where R is alkyl and R" is alkyl or hydrogen, toproduce a mixture of sultones and alkenesulfonic acids, which mixture isthen treated to convert the sultones to sulfonates. Examples of othersulfate or sulfonate detergents are paraffin sulfonates, such as thereaction products of alpha olefins and bisulfates (e.g. sodiumbisulfate), e.g., primary paraffin sulfonates of about 10-20, preferablyabout 15-20 carbon atoms; sulfates or higher alcohols; salts ofa-sulfofatty esters (e.g. of about 10-20 carbon atoms, such as methyla-sulfomyristate or a-sulfotallowate).

Examples of sulfates of higher alcohols are sodium lauryl sulfate,sodium tallow alcohol sulfate, Turkey Red Oil or other sulfated oils, orsulfates of monoor diglycerides of fatty acids (e.g. stearicmonoglyceride monsulfate), alkyl poly (ethenoxy) ether sulfates such asthe sulfates of the condensation products of ethylene oxide and laurylalcohol (usually having one to five ethenoxy groups per molecule);lauryl or other higher alkyl glyceryl ether sulfonates; aromatic poly(ethenoxy) ether sulfates such as the sulfates of the condensationproducts of ethylene oxide and nonyl phenol (usually having one to sixoxyethylene groups per molecule).

The suitable anionic detergents include also the acyl sarocosinates(e.g. sodium lauroylsarcosinate) the acyl esters (e.g. oleic acid ester)of isethionates, and the acyl N-methyl taurides (e.g. potassium N-methyllauroylor oleyl tauride).

The most highly preferred water-soluble anionic detergent compounds arethe ammonium and substituted ammonium (such as mono-, diandtriethanolamine), alkali metal (such as sodium and potassium) andalkaline earth metal (such as calcium and magnesium) salts or the higheralkyl benzene sulfonates, olefin sulfonates, the higher alkyl sulfates,and the higher fatty acid monoglyceride sulfates. The particular saltwill be suitably selected depending upon the particular formulation andthe proportions therein. Nonionic surface-active agents include thosesurface-active or detergent compounds which contain an organichydrophobic group and a hydrophilic group which is a reaction product ofa solubilizing group such as carboxylate, hydroxyl, amide or amino withethylene oxide or with the polyhydration product thereof, polyethyleneglycol.

As examples of nonionic surface-active agents which may be used theremay be noted the condensation products of alkyl phenols with ethyleneoxide, e.g., the reaction product of isooctyl phenol with about six to30 ethylene oxide units; condensation products of alkyl thiophenols with[0 to 15 ethylene oxide units; condensation products of higher fattyalcohols such as tridecyl alcohol with ethylene oxide; ethylene oxideaddends of monoesters of hexahydric alcohols and inner ethers thereofsuch as sorbitan monolaurate, sorbitol monooleate and mannitalmonopalmitate, and the condensation products of polypropylene glycolwith ethylene oxide.

Cationic surface-active agents may also be employed. Such agents arethose surface-active detergent compounds which contain an organichydrophobic group and a cationic solubilizing group. Typical cationicsolubilizing groups are amine and quaternary groups.

As examples of suitable synthetic cationic detergents there may be notedthe diamines such as those of the type RNHQl-LNH wherein R is an alkylgroup of about l2 to 22 carbon atoms, such as .N-Z-aminoethyl stearylamine and N-2- aminoethyl myristyl amine; amide-linked amines such asthose of the type RCONHC l-LNH where R is an alkyl group of about nineto 20 carbon atoms, such as N-2-amino ethylstearyl amide and N-aminoethyl myristyl amide; quaternary ammonium compounds wherein typicallyone of the groups linked to the nitrogen atom is an alkyl group of about12 to l8 carbon atoms and three of the groups linked to the nitrogenatom are alkyl groups which contain one to three carbon atoms, includingsuch one to three carbon alkyl groups bearing inert substituents, suchas phenyl groups, and there is present an anion such as halogen,acetate, methosulfate, etc. Typical quaternary ammonium detergents areethyl-dimethylstearyl ammonium chloride, benzyl-dimethyl-stearylammonium chloride, benzyl-dimethyl-stearyl ammonium chloride, trimethylstearyl ammonium chloride, trimethyl-cetyl ammonium bromide,dimethyl-ethyl dilauryl ammonium chloride, dimethyl-propylmyristylammonium chloride, and the corresponding methosulfates and acetates.

Examples of suitable amphoteric detergents are those containing both ananionic and a cationic group and a hydrophobic organic group, which isadvantageously a higher aliphatic radical, e.g. of 1020 carbon atoms.Among these are the N- longchain alkyl aminocarboxylic acids (e.g. ofthe formula the N-long-chain alkyl iminodicarboxylic acids (e.g. of theforwhere R is a long-chain alkyl group, e.g. of about -20 carbons, R isa divalent radical joining the amino and carboxyl portions of an aminoacid (e.g. an alkylene radical of one to four carbon atoms), M ishydrogen or a salt-forming metal, R is a hydrogen or another monovalentsubstituent (e.g. methyl or other lower alkyl), and R and R aremonovalent substituents joined to the nitrogen by carbon-to-nitrogenbonds (e.g. methyl or other lower alkyl substituents). Examples ofspecific amphoteric detergents are N-alkyl-betaaminopropionic acid;N-alkyl-beta-iminodipropionic acid, and N-alkyl, N,N-dimethyl glycine;the alkyl group may be, for example, that derived from coco fattyalcohol, lauryl alcohol, myristyl alcohol (or a lauryl-myristylmixture), hydrogenated tallow alcohol, cetyl, stearyl, or blends of suchalcohols. The substituted aminopropionic and iminodipropionic acids areoften supplied in the sodium or other salt forms, which may likewise beused in the practice of this invention. Examples of other amphotericdetergents are the fatty imidazolines such as those made by reacting along chain fatty acid (e.g. of 10 to carbon atoms) with diethylenetriamine and monohalocarboxylic acids having two to six carbon atoms,e.g. l-coco-S- hydroxethyl-S-carboxymethylimidazoline; betainescontaining a sulfonic group instead of the carboxylic group; betaines inwhich the long-chain substituent is joined to the carboxylic groupwithout an intervening nitrogen atom, e.g. inner salts ofZ-trimethylamino fatty acids such as Z-trimethylaminolauric acid, andcompounds of any of the previously mentioned types but in which thenitrogen atom is replaced by phosphorus.

Water-soluble builder salts may also be present, in the usualproportions, in the detergent formulations when heavy-duty cleaning isdesired. These salts include phosphates and particularly condensedphosphates (e.g. pyrophosphates orv tripolyphosphates), as well asorganic builders such as salts of nitrilotriacetic acid or ethylenediamine tetracetic acid. Sodium and potassium salts are preferred.Specific examples are sodium tripolyphosphate, potassium pyrophosphate,sodium hexametaphosphate, sodium tetraborate, sodium silicate, salts(e.g. Na salt) of methylene diphosphonic acid, trisodiumnitrilotriacetate, or mixtures of such builders, including mix tures ofpentasodium tripolyphosphate and trisodium nitrilotriacetate in a ratio,of these two builders, of 1:10 to 10:1, e.g. 1:1. The proportions ofbuilder salt may be, for example, 50 parts or more (e.g. 50 to 1,000parts) per 100 parts of detergent.

The detergent formulation may also contain other ingredients. Amongthese are soil-suspending agents such as sodium carboxymethyl celluloseor polyvinyl alcohol, preferably both, or other soluble polymericmaterials, such as methyl cellulose (the amount of suspending agentbeing, for example, in the range of about 1/20 percent to 2 percent);antioxidants such as 2,6-di-tert-butylphenol, or other phenolicantioxidant materials (e.g. in amounts in the range of about 0.001 to0.1 percent); coloring agents and optical brightening agents orfluorescent dyes in amounts in the range of, for example, about 1.20percent to 1/2 percent. Among the optical brightening agents are suchcompounds as the fluorescent dyes of the stilbene type, e.g. sodium2-sulfo-4-(2-naphtho-1 ,2 triazole) stilbene; disodium4,4-bis(4-anilino--morpholine-striazin-2-yl-amino) stilbenedisulfonate;or disodium 4,4-bis(4,6-dianilino-s-triazin-Z-yl-amino)2,2'-stilbenedisulfonate; or ofthe oxazole type, e.g. having a l-phenyl 2 benzoxazole ethylenestructure. In preparing aqueous liquid formulations in particular,hydrotropic materials such as lower alkyl aryl sulfonates, e.g. sodiumtolueneor xylene-sulfonate, may be used where desired or necessary; ingeneral, these materials are present in minor amounts, usually in therange of about l/2 to 15 percent (e.g. 10 percent) of the total liquid'composition.

One may also add known germicidal ingredients to the detergentcompositions. These include halogenated carbanilides, e.g.trichlorocarbanilide, halogenated salicylanilide, e,g.tribromosalicylanilide, bisphenols. e.g. hexachlorophene, halogenatedtrifluoromethyldiphenyl urea, zinc salt of lhydroxy-Z-pyridinethione andthe like (e.g. in amounts in the range of about l/50 percent to 2percent).

Opacifiers, perfumes, and antitarnishing agents may also be included inthe detergent compositions containing the novel products of thisinvention, as may oxygenand chlorinereleasing bleaches, such as sodiumperborate or sodium or potassium dichloroisocyanurate. Heavy-dutydetergent compositions containing the new products may also containsodium bromide (e.g. in amount of 0.1 to 1 percent) to improve thebleaching effect of sodium hypochlorite present in the wash water.

The detergent compositions containing the novel products of thisinvention may also contain enzymes to assist in the removal of stains.Particularly important among these are the proteolytic enzymes whichsuch materials as pepsin, trypsin, chymotrypsin, papain, bromelin,colleginase, keratinase, carboxylase, amino peptidase, elastase,substilisia and aspergillopepidase A and B. Among commercially availableenzymes are Alcalcase and Maxatase. The enzyme is preferably present inpowered form and is admixed into the detergent formulation, typically inamount of about 0.001 percent to 4 percent of the total formulation,preferably about 0.05-1 percent. The combination of the novel productsof this invention with enzymes yields particularly efficacious results.The enzyme-containing product can be used in cool or tepid water or inhot water.

The manufacture of detergent products in bar form, e.g. toilet bars andlaundry bars, from olefin sulfonate detergents is described in BelgianPat. No. 698,280. The novel hydroxy ether sulfonate compounds of thisinvention may each be substituted for the olefin sulfonates in the sameproportions in each of the general and specific formulations set forthin that patent. The same or similar processing techniques may be usedfor blending the ingredients and for making the bars.

ln the manufacture of oral preparations, the novel materials of thisinvention may be incorporated in toothpastes, dental creams, toothpowders, liquid dentifrices, mouth washes or rinses, dental chewinggums, lozenges or troches. Thus, in a tooth paste the composition maycomprise some 20-75 percent of dental polishing agent, together withwater. a humectant such as glycerol, and a gelling agent such as sodiumcarboxymethyl cellulose. Fluorides such as stannous fluoride may bepresent. In general, the novel hydroxy ether sulfonate compounds of thisinvention may each be substituted for the olefin sulfonates in each ofthe general and specific formulations set forth in the applications ofBouchal and Salzmann, Ser. No. 579,497 and of Rubinfeld and Levinsky,Ser. No. 579,524 now abandoned, each filed Sept. 15, 1966.

Shampoo formulations may comprise simple dispersions of the newdetergent materials of this invention in water, e.g. in the form ofalkanolammonium salts thereof, or combinations containing minorproportions of foam-boosting agents such as fatty acid (e.g.lauric/myristic) monoor di-ethanolamides or the correspondingisopropanolamides, or amine oxides such as lauryl dimethylamine oxide.Other surface active detergents such as soaps and sodium lauryl sulfatemay also be present.

EXAMPLE 1 Preparation of:

0.3 grams of sodium is dissolved in ml. of allyl alcohol and 48 grams(0.2 moles) of 1,2-hexadecane epoxide is added and the mixture refluxedfor 4.5 hours. When the reaction begins, the temperature of therefluxing system is 966 C., the temperature rising slowly during thecourse of the reaction. After the reaction mixture has refluxed for 2.5hours the temperature has risen to l00.6 C.; no further rise intemperature is observed. The course of the reaction is followed by meansof gas phase chromatography. The column used is a 2-foot Silicon-rubber"column (2 percent SE-30 on Chromosorb W). THe temperature is 100 C. whenthe sample is injected, followed by a programmed temperature rise of 15C. per minutes. The original epoxide appears as a peak after 6.6 minutesin the column. After 3.5 hours of reflux the epoxide peak has almostdisappeared, while the formation of the product can be seen as a strongpeak that appears after 9 minutes in the column. After 4.5 hours ofreflux the epoxide peak has disappeared completely.

After neutralization with concentrated hydrochloric acid the excessalcohol is evaporated and the residue is distilled under vacuum. Thisyields 43.5 g. (73 percent yield) of a colorless liquid, boiling rangel55l56 C./O.8 mm. Hg, freezing point 32.5 C.

Elemental analysis of the compound corresponds to the formula:c,,1-i,,,.0

The infrared spectrum has the following characteristic absorptions:

Strong band due to -H of an alcohol Weak hand due to a carbon-carbondouble bond.

2.9 microns 6.04 microns 10.05 microns Two strung hands due to aterminal vinyl group. 10.75 microns 8.9-9.2 microns Strong. broad banddue to secondary hydroxyl and ether groups.

Sulfonation of C I-I29 CH-CHr O CHz- CH=CH2 The unsaturated hydroxyetherproduced above is sul-- fonated by dissolving 15 grams of theunsaturated intermediate compound (0.05 moles) in 25 milliliters ofmethanol, adding 5.2 grams of sodium bisulfite dissolved in milliliterswater, and adding 0.5 milliliters of tertiary butyl perbenzoate as acatalyst. This mixture is stirred at 75 C., and the reaction is followedby gas phase chromatography as above, this time by watching thedisappearance of the peak at 9 minutes which is due to the unsaturatedhydroxyether. After 3 hours at 75 C., most of the unsaturatedhydroxyether has reacted. After 5 hours of reaction, the mixture iscooled to room temperature and then stirred into 300 milliliters ofacetone. The white solid which precipitates is filtered off andrecrystallized from a water/methanol mixture. After drying, 16.0 g. of awhite solid is obtained (80 percent yield). A melting point could not beobtained since decomposition occurs around 175 C.

The infrared spectrum and elemental analysis correspond to the followingstructure:

(])H CuHznCH-CHz-O-CHzCHzCHzS OaNa EXAMPLE ll Sulfonation and isolationis carried out as in example 1 using 1 1.5 g. of sodium bisulfitedissolved in 22 ml. of water and adding the solution to a solution of 30g. of the above unsaturated hydroxyether in 50 ml. of methanol. One ml.of tertiary butyl perbenzoate is added as a catalyst. The isolated product, by infrared spectrum and elemental analysis, has the structure:

This product decomposes at about 1 75 C.

EXAMPLE lll Example I is again repeated using an equivalent amount of1,2-dodecane epoxide. The resultant unsaturated ether product has aboiling point of 1 17 C./O.5 mm. Hg and has the formula:

Sulfonation as in example I yields a product of the formula:

EXAMPLE-1V The reaction of hexadecanel ,2-epoxide with allyl alcohol,

using boron trifluoride etherate as catalyst To 1 16 grams allyl alcoholcontaining 0.5 milliliters boron trifluoride diethyl etherate is added240 grams 1 mole) of the epoxide dropwise from an addition funnel whilestirring rapidly. The addition of the epoxide is complete in 20 minutes;during the reaction the temperature rises from 25 to C. As gaschromatogram performed as described under example I shows that all theepoxide has reacted. After the excess allyl alcohol has been removed bydistilling at reduced pressure, a sample of the reaction product ischromatographed on a 6 feet DEGS column (20 percent Diethylene GlycolSuccinate on Chromosorb W); temperature 220 C., isothermal.

Two peaks are observed, at 10.6 minutes and at 12.5 minutes. This showsthat the reaction had yielded two products, via the reaction:

CHzOH CHzOH EXAMPLE V Example 1V is repeated except that the twoisomeric alcohols are separated by the chromatographic proceduredescribed in example 1V and the pure primary unsaturated alcohol productis sulfonated as in example 1V.

EXAMPLE VI The general procedure of example 1V is followed using 8.6 g.(0.1 mole) of l-pentene-S-ol containing 2 drops of boron trifluorideetherate (diethyl), and adding dropwise while stirring, 18.4 g. (0.1mole) of dodecane-1,2-epoxide. Two main products are formed (Le. aprimary and a secondary alcohol) as shown by the gas chromatogram. Theproducts are isomeric and have the structures:

11 CH;(CH2)nCH-O(CH2)3CH=CH2 (30%) GHiOH The relative amounts aredetermined by calculations based upon the areas under the peaks obtainedin the chromatogram. The mixture has a boiling point range of l40146 C.at 0.4 mm. Hg. The infrared spectrum is shown in FIG. 1.

The mixture produced above is sulfonated using g. of

said mixture and a solution of 4.55 g. Nal-lSQ and 0.25 ml. of

tertiary butyl perbenzoate in 10 ml. of methanol and 7.5 ml. of.

water. Stirring is carried out for 1% hours at 135 C. After cooling. 200ml. of acetone are stirred into the mixture. A white precipitate formswhich is filtered and dried. The yield is 12 g. (85 percent).

The sulfonated mixture contains:

OH and 30% CH3(CH2)9CH- 0(CH2) SOJNa CH2 OH EXAMPLE V" 16.3 g. (0.05moles) of the above mixture of unsaturated a1- cohols, 16 ml. methanol,0.3 ml. t-butyl perbenzoate, 5.7 g. (0.055 moles) of sodium bisulfitedissolved in 11.5 ml. of water are stirred for 1 hour at 135 C. Then themixture is poured into acetone and the resultant precipitate is filteredoff and dried. Yield is 16.59 g. (77 percent). The product is a mixtureof:

70% onnoHzmt ln-cm-ocnms 01m 0H- and 30% CHa(CH2)ta H 0(CH2)s S OsN CH2OH EXAMPLE V1" The procedures of examples V1 and V11 are repeatedinsofar as the production of the unsaturated alcohols is concerned. Ineach case, the mixture is separated into the individual componentisomers by a gas phase chromatographic column separation technique. Theresultant four products (two isomers of example V1 and two isomers ofexample V11) are sulfonated in examples V1 and Vll respectively usingequivalent amounts of reactants.

EXAMPLE [X The hydroxy ether sulfonates prepared in examples 1 to 111are tested for their detergency relative to linear tridecyl benzenesulfonate, a commercially available detergent. The detergency of thematerials produced in examples 1 to 111 relative to the control isinvestigated in both soft and hard water and both hot and cold water.

The results of the Spangler soil detergency tests are shown in table 1below:

TABLE 1 Spangler Soil* Detergency Test Results ARd" (Soil Removal)Temperature and Control Water Hardness Ex. 1 Ex. 2 Ex. 3 LTBS) (lineartridecyl sulfonate) 70 F.,N.B.'"Tap +193 +l9.6 +l7.6 +181 (90 p.p.m.) 70F.. +160 +l4.9 +1l.2 +9.3 (:00 p.p.m.) 120 F., N.B. Tap +19.7 +201] +174+193 120 F., +l6.$ +153 +118 +ll.6 (300 p.p.m.)

The Spangler Soil test is carried out using cotton percale swatches (3inches by 6 inches) soiled with synthetically prepared sebum soilemploying 1.5 g. of test detergent and 1 liter of water; the wash cycleis 10 minutes at 100 c.p.m. agitation followed by 5 minutes rinse insame water used in wash. The test detergent is comprised of:

15 percent active sulfonate 35 percent sodium tripolyphosphate Theprevious example IS repeated using 0.15 moles of the alcohol and 0.1mole of hexadecane-l,2-epoxide. The isolated unsaturated alcohol mixturehas a boiling point range of 178184 C. at 0.6 mm. Hg. The molecularweight is 326. The product is a liquid at room temperature and contains:

50 percent sodium sulfate a value indicates soil removal.

'New Brunswick, New Jersey.

The results shown above indicate an unexpectedly excellent detergency inhard water and soft water, both cold and hot, as compared to thecommercial detergent linear tridecyl benzene sulfonate. Accordingly,this exemplifies the unusually good detergency properties of the novelhydroxy ether sulfonates of the present invention.

EXAMPLE X The hydroxy ether sulfonate produced in example 1 is testedfor fabric-softening ability in a towel tests. The water employed in theforegoing softening test is l20 F., New Brunswick, N..l., tap water. Acontrolled detergent composition is prepared by combining 40 grams ofsodium tripolyphosphate and I grams of active ingredient of lineardodecyl benzene sulfonate. Ten grams of the hydroxy ether sulfonateproduced in example I is also added to 40 grams of the detergent buildersodium tripolyphosphate.

On a scale rating softness from 1 to l0, being maximum softening of thefabric, the control containing the detergent builder and commercialdetergent produces a result of 1, while the composition containing thehydroxy ether sulfonate in accordance with the present inventionproduces a result of 8.

This test, therefore indicates that the hydroxy ether sul-' fonates ofthe present invention, in addition to possessing excellent detergency,also possess excellent fabric-softening characteristics.

EXAMPLE XI In accordance with the procedure of example "I, the followinghydroxy ether sulfonates are prepared:

In all cases. the hydroxy ether sulfonate is prepared by reacting thecorresponding long-chain epoxide with allyl alcohol to form theunsaturated hydroxy ether intermediate with sulfonation of theunsaturated intermediate with sodium, potassium, or ammonium bisulfiteto produce the desired hydroxy ether sulfonate.

EXAMPLE XII The hydroyether sulfonate products of examples lV, VI andVII are tested as in example lX 'with the following results:

TABLE [I Spangler Soil Detergency Test Results Temperature and ANd (SoilRemoval) Control water hardness Ex. VI Ex. Vll (LTBS) Ex. lV

70 F. ma. Tap) 10 F. 300 (p.p.m.) 120 F. (N.B. Tap) 120 F. (300 p.p m.)

Again the outstanding overall performances in both hot and cold water atboth hardnesses of these products is demonstrated.

EXAMPLE Xlll CH; CH;

EXAMPLE XlV Example is repeated except that in the sulfonation ammoniumbisulfite is used in place of the sodium salt. The correspondingammonium compound is produced.

EXAMPLE XV Example I is repeated except that the final product isacidified in water, the aqueous solution extracted with alcohol and theacid form neutralized with triethanolamine. Isolation is done similarlyas in example I by precipitation with acetone.

While various embodiments of the present invention have been describedby reference to the foregoing examples it is to be understood that thepresent invention is in no way to be deemed as limited thereto butshould be construed so as broadly as all or any equivalents thereof.

What is claimed is:

1. Novel compounds which in the free acid form have the formula:

Ltd.

wherein:

l. R, is a straight or branched higher alkyl group of C to C 2. Rz is astraight or branched alkylene of C,, to C 3. R to R, are, independently,hydrogen, straight or branched alkyl of C, to C,,,;

4. Z is oxygen or sulfur;

5. x and y have the values 0 or 1 and .r-l-y=l; and

6. when x equals 0 the depicted OH group is attached directly to C.

. Compounds of claim 1 wherein Z is oxygen.

. Compounds of claim 1 wherein Z is sulfur.

. Compounds of claim 2 wherein R, is C alkyl.

. Compounds of claim 2 wherein R, is C alkyl.

. Compounds of claim 2 wherein R, is C, alkyl.

. Compound of claim 4 wherein R R and R are hydrogen, and

. R is C, alkylene.

. Compound of claim 5 wherein R,,, R and R, are hydrogen, and

. R is C, alkylene.

. Compound of claim 5 wherein 1. R R, and R are hydrogen, and

2. R is C, alkylene.

10. Compound of claim 9 wherein 1. R R and R are hydrogen, and

2. R is C,, alkylene.

11. A process for producing the compounds of claim 1 which comprisesreacting a 1,2-epoxy C to C alkane with a C to C, olefinicallyunsaturated alcohol or thiol and thereafter sulfonating the resultantproduct with sodium bisulfite in the presence of a peroxide initiator.

12. A process as defined in claim 11 wherein from 0.00l percent to about10 percent of a catalyst is employed in the epoxy-alcohol reaction step.

13. A process as defined in claim 12 wherein the said catalyst issodium.

14. Compounds of claim 1 wherein .-r equals 1.

15. Compounds of claim 1 wherein y equals 1.

2. R2 is a straight or branched alkylene of C3 to C12;
 2. CompoundS ofclaim 1 wherein Z is oxygen.
 2. R2 is C3 alkylene.
 2. R2 is C3 alkylene.2. R2 is C5 alkylene.
 2. R2 is C3 alkylene.
 3. Compounds of claim 1wherein Z is sulfur.
 3. R3 to R7 are, independently, hydrogen, straightor branched alkyl of C1 to C10;
 4. Z is oxygen or sulfur;
 4. Compoundsof claim 2 wherein R1 is C10 alkyl.
 5. Compounds of claim 2 wherein R1is C14 alkyl.
 5. x and y have the values 0 or 1 and x+y 1; and
 6. when xequals 0 the depicted OH group is attached directly to C*.
 6. Compoundsof claim 2 wherein R1 is C16 alkyl.
 7. Compound of claim 4 wherein 8.Compound of claim 5 wherein
 9. Compound of claim 5 wherein
 10. Compoundof claim 9 wherein
 11. A process for producing the compounds of claim 1which comprises reacting a 1,2-epoxy C8 to C32 alkane with a C2 to C10olefinically unsaturated alcohol or thiol and thereafter sulfonating theresultant product with sodium bisulfite in the presence of a peroxideinitiator.
 12. A process as defined in claim 11 wherein from 0.001percent to about 10 percent of a catalyst is employed in theepoxy-alcohol reaction step.
 13. A process as defined in claim 12wherein the said catalyst is sodium.
 14. Compounds of claim 1 wherein xequals
 1. 15. Compounds of claim 1 wherein y equals 1.